CH3A4, Polymer Chemistry 2002/2003

www.warwick.ac.uk/polymers
 CH3A4, Polymer Chemistry 2002/2003

• Copolymers
• Ionic Polymerisation
• Statistical Copolymers
CH3A4, Polymer Chemistry Dave Haddleton
2002/2003

Lecture 1

Introduction

Discussion of polymers in everyday use

– structure/property correlation

Brief description of copolymers

– statistical, block, graft copolymers
 Books
Principles of Polymerisation
G Odian
• Mayo
Polymer Equation
Synthesis
P Rempp and E W Merrill

Polymers: Chemistry & Physics of Modern Materials

J M G Cowie

Polymer Chemistry : An Introduction

G Challa

Introduction to Polymers
R J Young and P A Lovell
 Need to Know from Year 2

• Viscosity equations
• Mark-Houwink equation
• Scheme for Free radical Polymerisation
• Plastics • Mobile phones
• Paint • Shampoo
• Adhesives • Cosmetics
• Fibres/Fabrics • Optics
• Tyres • CD,s
 Copolymers

• Statistical
• Block
• Graft
• Alternating
• Terpolymers
When the two monomers are arranged in an alternating
fashion,
the polymer is called, of course, an alternating copolymer:

-A-B-A-B-A-B-A-B-A-B-
In a random copolymer, the two monomers may
follow in any order:
-A-A-B-A-B-B-B-A-B-A-A-B-

In a block copolymer, all of one type of monomer are grouped

together, and all of the other are grouped together. A block
copolymer can be thought of as two homopolymers joined
together at the ends
 T a c tic ity , P o ly m e r s te re o c h e m is try

G e n e ra lly , ta c tic ity a p p lie s to a d d itio n p o ly m e rs w ith o n e

n o n -h y d ro g e n s u b s titu te a tta c h e d to th e
c a rb o n c h a in fo r e a c h m o n o m e r u n it:

T a c tic ity h a s to d o w ith w h ic h s id e o f th e c h a in th e R

g ro u p is p la c e d :

Is o ta c tic

N o tic e th a t a ll o f th e R g ro u p s lin e u p o n th e s a m e s id e .

S y n d io ta c tic

N o tic e th a t th e R g ro u p s a lte rn a te fro m s id e to s id e .

A ta c tic

T h e s id e to s id e p o s itio n in g is ra n d o m .
Lecture 2

Revision of polymers in solution

viscosity equations, Mark-Houwink equations

Polymers in the solid state, Tg and Tm,

physical meaning of Tg

Tg of copolymers, calculation of Tg with respect

to polymer composition

Revision of free radical homopolymerisation

 Polymers in Solution

• When we add a polymer to a solvent

• A) Polymer swells to a gel

• B) Dissolves to a viscous solution

• Usually into a random coil or sometimes

more rod like
 Viscosity equations

Relative viscosity

 = /0

Specific viscosity

sp = (-0)/ 0

Reduced viscosity

red = 1/c*sp

Intrinsic viscosity

 = red at [ ] = 0
 M o le c u la r m a s s o f p o ly m e r s

N u m b e r -a v e r a g e m o le c u la r m a s s

O b t a in e d b y w e ig h t in g e a c h m o la r m a s s b y t h e n u m b e r o f m o le c u le s o f t h a t
m o la r m a s s p r e s e n t in t h e m o le c u le .

 NiMi 1
Mn    NiMi
 Ni N
W e ig h t-a v e ra g e m o le c u la r m a s s

Mw 
 NiMiMi
 NiMi
Z -a v e ra g e m o la r m a s s

Mz 
 NiMiMiMi
 NiMiMi
M o le c u la r w e ig h t d is trib u tio n o r P o ly d is p e rs ity in d e x (M W D o r P d i)

P d i = M w /M n
 M o le c u la r m a s s o f p o ly m e r s

N u m b e r -a v e r a g e m o le c u la r m a s s

O b t a in e d b y w e ig h t in g e a c h m o la r m a s s b y t h e n u m b e r o f m o le c u le s o f t h a t
m o la r m a s s p r e s e n t in t h e m o le c u le .

 NiMi 1
Mn    NiMi
 Ni N

W e ig h t-a v e ra g e m o le c u la r m a s s

Mw 
 NiMiMi
 NiMi

Z -a v e ra g e m o la r m a s s

Mz 
 NiMiMiMi
 NiMiMi
 Polymers in the solid state

• Crystalline
• Glassy

• Not all polymers can crystallise

• None are 100% crystalline

• (look at USM web page for movie)

Tg < Tm

T g /T m = 0 .5 f o r s y m m e tr ic a l p o ly m e r s

e .g .

*
* n
Cl Cl

T g /T m = 0 .7 5 f o r u n s y m m e tr ic a l
p o ly m e rs

e .g .

*
* n

OAc
 Free Radical Polymerisation

 Widely used industrially

 Advantages:

- Very Robust Technique

- Wide range of monomers and functionalities

Almost anything with a double bond

- Wide range of operating conditions

- Aqueous Media: Emulsion polymerisation

 Disadvantages

- Highly non-selective reaction

- Non-trivial product control

 Ge ne ra l re ma rks a bout Ra dica l P olyme ris a tion

 The life time of e a ch ra dica l is ve ry s hort. Initia tion,

propa ga tion, tra ns fe r a nd te rmina tion a ll ta ke pla ce
in a s e cond or s o. The re fore the [ra dica l] is a lwa ys
ve ry low a nd in mos t ca s e s is e xpe rime nta lly
ina cce s s ible .

 P roba bility of a ny tra ns fe r is us ua lly low. Howe ve r,

a s e a ch cha in ma y involve 100-1,000,000 s te ps
tra ns fe r will occur for e a ch kine tic cha in.

 Tra ns fe r is us e d to re gula te Mwt to obta in s hort

polyme r cha ins .

 Tra ns fe r to polyme r will re s ult in polyme r bra nching.

 INITIATION

I* + M  IM* ki

PROPAGATION

IM* + M  IMM* kp1

IMn* + M  IMnM* kpn

 O O
O
O O
O

O O
O
O + O
O C
O

O
O
O
O
O C + O
O O C
OAc OAc
O

Propagation

O Combination
O OAc
O n C I
O n n
OAc OAc
OAc
 Copolymerisation

• If we have 50 mol% MMA and 50 mol%

Styrene and leave the reaction to 50%
conversion.
• What is the composition of the polymer?
• What is the composition of the monomer?
• What is the Tg of the polymer produced?
 O
* O
O n *
O

A
O
* O
O n *
O

Both A and B benefit from H-bonding between the chains although not nearly as much as
if they were amides. There is probably not enough H-bonding for A to be crystalline so
will not have a Tm. Polymer B has the aromatic moiety in the backbone restricting
rotation and thus increasing the Tg and promoting crystallisation. Thus A will have the
lower Tg and B will have the higher melting temperature.

N.B. Find out the empirical relationship between Tg and Tm.

Tg of Poly(methyl methacrylate) = 105 oC and poly(butyl acrylate) = -40oC (Actual values might vary from
book to book).

So if we use Tg = Tg1*w1+Tg2*w2
Remember we need wt fraction not mole fraction. MWt of PMMA = 100 and PBA = 128.

378 233 wt frac A wt frac B Tg K Tg oC

90 10 0.875486 0.124514 359.9 86.9

30 70 0.250836 0.749164 269.4 -3.6
50 50 0.438596 0.561404 296.6 23.6
10 90 0.079872 0.920128 244.6 -28.4

Using the other formula

378 233 wt frac A wt frac B Tg K Tg oC

90 10 0.875486 0.124514 350.8 77.8

30 70 0.250836 0.749164 257.8 -15.2
50 50 0.438596 0.561404 280.1 7.1
10 90 0.079872 0.920128 240.4 -32.6
Initiation

Initiator  2R

R + Monomer 1 (M1)  RM1

Rate = k1[M1][ R]

R + Monomer 2 (M2)  RM2

Rate = k2[M2][ R]

 Statistical Copolymerization

• RM1 + M1  RM1M1
Rate = k11[RM1][M1]

• RM1 + M2  RM1M2
Rate = k12[RM1][M2]

• RM2 + M1  RM2M1
Rate = k21[RM2][M1]

• RM2 + M2  RM2M2
Rate = k22[RM2][M2]
The rate of monomer disappearance is given by:

-d[M1]/dt = k11[M1*][M1] + k21[M2*][M1]

-d[M2]/dt = k12[M1*][M2] + k22[M2*][M2]

Steady state approximation

k12[M1*][M2] = k21[M2*][M1]

[M1*]/ [M2*] = k21[M1] k12[M2]

The relative rates of comonomer incorporation then
reads

d[M1]/d[M2] = k11[M1*][M1] + k21[M2*][M1]

k12[M1*][M2] + k22[M2*][M2]

divide both by [M2*] and rearrange

d[M1]/d[M2] = [M1] {k11/ k12 [M1] +[M2] }

[M2] {k22/ k21 [M2] +[M1] }
 Reactivity ratios

• r1 = k11
k12

• r2 = k22
k21
 Statistical Copolymerization

• r1 characterizes the reactivity of the 1

radical with respect to the two monomers 1
and 2

• If r1 > 1 then homopolymerization growth is

preferred
• If r1 = 0 then only reaction with 2 will occur
 Statistical Copolymerization

• Fa is the amount of monomer A in the

POLYMER

• fa is the amount of monomer A in the

monomer feed

• Fa + Fb = 1; fa + fb = 1
Mole fraction of monomer A in feed

fa = [M1]/{[M1] + [M2]}
 Reactivity ratios

• r1 = k11
k12

• r2 = k22
k21
 Copolymer equation

• Incorporate reactivity ratios and use mole

fractions

F1 = r1f12 + f1f2

r1f12 + r2f22 + 2f1f2

Reactivity ratios are monomer pair dependant
I.e. they are always the same for each monomer pair
 Assumptions

• Long Chain assumption i.e. initiation and

termination reactions can be ignored in the
calculation of copolymer composition
• Equal reactivity i.e rate is independent of
chain size
• Reactivity ratios are independent of dilution
• Reactivity ratios are independent of rate and
conversion
 Assumptions continued

• Reactivity ratios are independent of

inhibitors, retarder CTA’s and solvents
We now need to look at the effect of the
reactivity ratios on the copolymerisation
process.

We plot the composition of the polymer

as a function of the composition of the
monomer feed.
 Ideal Copolymerization

• ra * r b = 1
• A* and B* exhibit the same relative
reactivity towards B

• equation becomes
• Fa = rafa
rf + f
a a b
 Ideal Copolymerization

• Plot is around the diagonal

 Alternating copolymer

• rb = 0
 Ideal copolymer

1.0

0.8 A = styrene
Fa (polymer composition)

B = butadiene
ra = 0.75, rb = 1.3
0.6

0.4

0.2

0.0
0.0 0.2 0.4 0.6 0.8 1.0
fa (monomer composition)
 Alternating Copolymer

1.0

0.9 A = styrene
0.8
B = maleic anhydride
ra = 0.05, rb = 0.0
Fa (polymer composition)

0.7

0.6

0.5

0.4

0.3

0.2

0.1

0.0
0.0 0.2 0.4 0.6 0.8 1.0
fa (monomer composition)
 Rich in one monomer

1.0

0.8 A = vinyl acetate

Fa (composition of polymer)

B = styrene
ra = 0.01, rb = 50
0.6

0.4

0.2

0.0
0.0 0.2 0.4 0.6 0.8 1.0
fa (Composition of monomer)
 Quite typical copolymerisation

1.0

A = Acrylonitrile
0.8 B = Butadiene
Fa (polymer composition)

ra = 0.046, rb = 0.36
0.6

0.4

0.2

0.0
0.0 0.2 0.4 0.6 0.8 1.0

fa (monomer composition)
Determination of reactivity ratios

• Copolymerise at different monomer feed

ratios
• Obtain Fa vs fa data (E.g. 0.2, 0.4, 0.6…)
• Interpret data by a lineraization method
– Kelen-Tudos
– Fineman-Ross
 Linearization method

• Fineman Ross
• (see transparency)
• ra and rb not treated symmetrically
• Kelen-Tudos method probably most
common
 Factors that affect copolymer
reactivites
• Steric Factors
• Resonance stabilization of radical
• Polarity of the double bond
 Qe scheme

• Attempt to predict the reactivity of a

monomer towards a radical
• Use resonance and polarization parameters
• Similar to Hammett plots
• Rather Qualitiative
Penultimate effects
fa fb ra rb Fa fa Fa

0 1 0.25 2 0 0 0
0.1 0.9 0.25 2 0.051318 0.1 0.051318
0.2 0.8 0.25 2 0.10559 0.2 0.10559
0.3 0.7 0.25 2 0.163445 0.3 0.163445
0.4 0.6 0.25 2 0.225806 0.4 0.225806
0.5 0.5 0.25 2 0.294118 0.5 0.294118
0.6 0.4 0.25 2 0.370787 0.6 0.370787
0.7 0.3 0.25 2 0.460208 0.7 0.460208
0.8 0.2 0.25 2 0.571429 0.8 0.571429
0.9 0.1 0.25 2 0.726708 0.9 0.726708
1 0 0.25 2 1 1 1
 1
0.9
0.8
0.7
0.6
0.5 Series1
0.4
0.3
0.2
0.1
0
0 0.2 0.4 0.6 0.8 1
 Living/Ionic Polymerisation

• Anionic Polymerisation
• Cationic Polymerisation
• Ring Opening Polymerisation
• Living Radical Polymerisation
• Group transfer Polymerisation
 Living Polymerisation

• Method to prepare polymers with predetermined

Mn
• DP = [Monomer]/[Initiator]
• Narrow PDi (<1.20)
• Controlled functionality
• Block copolymers by various strategies
• No termination
• No Chain Transfer
 Anionic Polymerisation

• More selective than radical polymerisation

• Need electron withdrawing group attached to vinyl
group
• e.g. -CO2R, -CN, -Ph, -vinyl
• Invented in 1956 by Swarzc (Nobel Prize)
• Industrial use limited
• Blocks, stars, grafts
• Usually an organometallic initiator
 INITIATION

I* + M  IM* ki

PROPAGATION

IM* + M  IMM* kp1

IMn* + M  IMnM* kpn

Anionic Polymerisation of
Styrene
Anionic Polymerisation of dienes
Aggregation of Butyl Lithium
Ion-Pair formation
 Solvents

• Aprotic to prevent transfer to solvent and

termination
• Free of electrophilic impurities which will
react with ionic sites
• Dissolve both monomer and polymer
allowing heterogeneous polymerisation
 Solvents can vary in polarity

• e.g.
• alkanes
• cyclohexane
• benzene
• toluene
• thf, dimethoxyethane
Additives can be used to increase
polarity
e.g.
glymes CH3CH2CH2OCH2CH2OCH3

crown ethers
O
O O

O O

Effect of solvent on the anionic polymerisation of

styrene
Dielectric constant kp (apparent), l mol-1g-1
benzene 2.2 2
dioxane 2.2 5
thf 7.6 550
dme 5.5 3,800
 Anionic Polymerisation of
Acrylics
H
E.g. O O O
OMe OBu OBu

R C O
R O
Initiation O OMe
OMe
R OMe Good

O
+ MeO-
R

Bad
Anionic Polymerisation of MMA

Propagating end is an enol

OMe O OMe O

20% 80%
 Problems with Propagation

MeO O
O
CO2Me
CO2Me
CO2Me
CO2Me

Backbiting

CO2Me CO2Me
C O O
CO2Me CO2Me
OMe

Ketene formation
D e g re e o f P o ly m e ris a tio n = D p n

i.e . D p

D p n = [M ]/[I] @ 1 0 0 % c o n v e rs io n

M n = D pn x M 0

(M 0 = m a s s o f th e re p e a t u n it)

T h u s a p lo t o f M n v s % C o n v e rs io n is lin e a r fo r
a liv in g p o ly m e ris a tio n
 100

80

60
Mn

40

20

0 20 40 60 80 100

Conversion, %
Rate of Initiation = ki[I][M]

Rate of Propagation = kp[M*][M]

[M*] = [I]

Integration leads to,

ln[M]0/[M] = kp[M*]t

As the rate of termination = 0

[M*] is constant

Thus a plot of ln[M] 0/[M] vs t is linear

If Rate of initiation (Ri)  or > Rate of
Propagation (Rp)

and both Ri and Rp > Rate of termination (Rt)

(Ideally Rt = 0)

Then

PDi (MWD, Mn/Mw) is narrow and a Poisson

distribution.

PDi = 1+1/[DPn]

e.g. For a polymer with DPn = 100, PDi = 1.01

ln[M]0/[M] kp[Pol*]

time, s
Calculate Mn for Psty with BuLi
Calculate PDi
ln[M]0/[M] kp[Pol*]

time, s
 Propagation

• Dependant on ion-pair
• Anion
• Cation (or Gegen-ion)
• Solvent polarity
Effect of solvent polarity on
stereochemistry
Iso p re n e

t r a n s 1 ,4

c is 1 ,4

1 ,2

C o u n te r - io n s o lv e n t 1 ,4 - c i c 1 ,4 - t r a n s 1 ,2 3 ,4
Li p e n ta n e 94 0 0 6
th f 0 25 10 65
E t2O 0 50 5 45
Na p e n ta n e 0 40 7 50
K p e n ta n e 0 55 7 35
Termination
Living polymerisation No termination

Need solvent with no acidic protons

Benzene, toluene, thf GOOD

Alcohol, water, ketone, BAD

We require

 NO chain transfer to solvent

 NO coupling

 NO disprpotionation

We need highly pure solvents otherwise we will get chain

transfer to impurity!

If no chain transfer then we proceeds to 100% yield. After

100% is reached addition of further monomer will restart
the reaction
Termination with protic
impurities
Termination to functioanl
polymers
 Block copolymers

• Sequential Monomer Addition

• Multi-functional Initiators
Calculate Mn for Block
Copolymer
 GTP

• Initiator OSiMe 3 OSiEt3

OMe OMe

Typically 100:1 Initiator : Catalyst

Mn is linear with conversion

Mn = [initiator]/[monomer]
Block copolymers by sequential addition
Termination to give selected functionality.
 Group Transfer Polymerisation
• Polar Solvent
eg thf, glymes
• (Will not work in non polar solvents eg toluene, MWD
is 2)
• Catalysts
• Nucleophiles
• eg F-, HF2-, AcO-, CN-

• Gegen-ions

• large eg Bu N+, Et N+
4 4
 Mechanism of GTP

• Associative
• Dissociative
GTP Associative Mechanism
-
MeO OSiMe3 MeO O Nu
SiMe3
Nu-

MeO O

O MeO - -
Nu Nu
MeO SiMe3 Si
O O
MeO

O MeO
OSiMe3
MeO
+ Nu-
GTP Irreversible Dissociative
Mechanism
MeO O
MeO OSiMe3
+ Nu-
- + Nu SiMe3

Anionic Propagation

e.g. Nu- = F- then Me3Si-F

You have synthesised a statistical copolymer of n-butyl methacrylate (1, 0.15 moles
) and n-octyl methacrylate (2, 0.16 moles) by Group Transfer Polymerisation (GTP)
using methyl trimethylsilyl dimethylketene acetal (MTS, 3, 2.07 x 10-3 moles)) and
tetrabutylammonium fluoride (TBAF, 2.07 x 10-5 moles).

(a) Give equations and kinetic expressions to describe initiation and propagation.
(35%)

(b) What is the expected number average molecular mass (Mn) of your product?
(15%)
(c) Comment on reaction conditions you might choose, with reasons for your choice.
(25%)
(d) Discuss briefly how you would expect the product to differ from a similar copolymer
synthesised by free radical polymerisation, include examples of how you might
experimentally distinguish between the two.
(25%)
Suggest practical ionic initiators and solvents for the ionic polymerisation of

O
CN
O
CN
OMe
A clean dry solution of styrene (5 g) in 50 mL of thf was held at –70 oC. Sodium (1.0 g) and napthalene
(6.0 g) were stirred together in 50 ml of dry thf to form a dark green solution of sodium napthalide.
When 1.0 mL of this green solution was added into the styrene solution the latter turned red orange.
After a few minutes the reaction was complete. The colour was quenched by the addition of a few
drops of ethanol. The polymer was precipitated and washed .

What is the Mn of the polymer?

Explain the colour changes.
What is the theoretical PDI?
 Cationic Polymerisation

• Over 20 yrs old

• Industrial use in butyl rubber manafacture
• Copolymer of
• Active sites are carbenium or oxonium
-
A
+
O
R +
A -

Need electron donating groups to stabilise the cation

 Cationic polymerisation

• Usually reactive enough to make polymers

at very low temperatures
• However, inherently unstable, side
reactions
•
• in particular -proton elimination from
active end
Monomers for Cationic
Polymerisation
OR

OR OR
 Cationic polymerisation

• Usually no real molecular weight control

• Living cationic polymerisation would yield
controlled polymer geometries not available
from other methods.
 Cationic Initiation
Protonic acids with bulky anions
e.g. H2SO4, HClO4, FSO3H, etc, etc
H
+ A
+ C
HA OR OR

Lewis Acids
e.g SnCl4, AlCl3, BF3 when reacted with a nucleophile

e.g. BF3 + OH2 [H+BF3OH-]

Cationic Propagation

+ H
C
Termination in Cationic
Polymerisation

See http://www.psrc.usm.edu/macrog/index.htm
 Living cationic polymerisation

• 1980's Sawamoto and Higahimura theorised

that if the charge on the cation could be
decreased by a specific nucleophilic
interaction it may be stabilised towards -
proton elimination.
• 1984 1st example of living cationic
polymerisation
 Living cationic polymerisation
OR
• using HI/I2
• shortly afterwards HI/ZnX2 X= I, Br, Cl
• Mn  [M]/[I]
• Block copolymer by sequential addition
• Mn increases linearly with conversion
 Ring Opening Metathesis
Metathesis of alkenes
R1 R3
R1 R3

R2 R4
R2 R4

Ring Opening
Ring Opening Metathesis

* *
n

trans with W, cis with Mo

*
* n

polynorbonene
Ring Opening Metathesis
* *
n

Poly(dicyclopentadiene)

*
* n

Poly(acetylene)
 Ring Opening Metathesis
Catalysts
• Normally made in-situ

• WCl6/AlEt3
• MoCl5/AlEt3
 Ring Opening Metathesis
M

carbene

M
M

metallocyclobutane
 Living ROMP

tBuO N
W
tBuO

Good ROMP catalyst W or Mo

Bulky ligands
M-O and M=N ligands
 Living ROMP

• Metal needs to be in high oxidation state

• 4-coordinate alkylidene with bulky ligands
• this allows small substrates to attack
• change alkoxide to (CF3)2MeC.O increase
turnover for pentene from 2 to 1000
turnovers per minute
 Commercial use of ROMP
• Poly(norbornene)
• MoO3/alumina
• production for 20 years

• PDCP
• Reaction injection moulding
• 2 reactant streams
• high density of crosslinks
 ROMP in water

O
OR
n
*
OR
RO OR
 Overview of course

• Radical Copolymerization
• Living Polymerization
• Anionic Polymerization
• Cationic Polymerization
• ROMP
 Control of Polymer Structure

• Block copolymers
• Telechelic polymers
• Graft copolymers
• Star copolymers
• Narrow PDi polymers
When the two monomers are arranged in an alternating
fashion,
the polymer is called, of course, an alternating copolymer:

-A-B-A-B-A-B-A-B-A-B-
In a random copolymer, the two monomers may
follow in any order:
-A-A-B-A-B-B-B-A-B-A-A-B-

In a block copolymer, all of one type of monomer are grouped

together, and all of the other are grouped together. A block
copolymer can be thought of as two homopolymers joined
together at the ends
 Equations

• Instantaneous copolymer equation

• Fa vs fa plots
• Mn in living polymerisation
• PDi in living polymerisation
• Mn for block copolymers
• Molecular weight equations
• Viscosity equations
• Tg for copolymers
 M o le c u la r m a s s o f p o ly m e r s

N u m b e r -a v e r a g e m o le c u la r m a s s

O b t a in e d b y w e ig h t in g e a c h m o la r m a s s b y t h e n u m b e r o f m o le c u le s o f t h a t
m o la r m a s s p r e s e n t in t h e m o le c u le .

 NiMi 1
Mn    NiMi
 Ni N

W e ig h t-a v e ra g e m o le c u la r m a s s

Mw 
 NiMiMi
 NiMi

Z -a v e ra g e m o la r m a s s

Mz 
 NiMiMiMi
 NiMiMi
 Copolymer equation

• Incorporate reactivity ratios and use mole

fractions

F1 = r1f12 + f1f2

r1f12 + r2f22 + 2f1f2

Reactivity ratios are monomer pair dependant
I.e. they are always the same for each monomer pair
 Viscosity equations

Relative viscosity

 = /0

Specific viscosity

sp = (-0)/ 0

Reduced viscosity

red = 1/c*sp

Intrinsic viscosity

 = red at [ ] = 0
D e g re e o f P o ly m e ris a tio n = D p n

i.e . D p

D p n = [M ]/[I] @ 1 0 0 % c o n v e rs io n

M n = D pn x M 0

(M 0 = m a s s o f th e re p e a t u n it)

T h u s a p lo t o f M n v s % C o n v e rs io n is lin e a r fo r
a liv in g p o ly m e ris a tio n
 Characterisation methods

• GPC
• NMR
• FTIR
• DSC
• MALDI MS
• Gravimetry